Microextraction with polyethersulfone for bisphenol-A, alkylphenols and hormones determination in water samples by means of gas chromatography–mass spectrometry and liquid chromatography–tandem mass spectrometry analysis

• The effectiveness of PES tubes for the extraction of some EDCs from aqueous samples.
• Optimization of the extraction and liquid desorption conditions.
• Quantification by both GC–MS, through a previous derivatization, and LC–MS/MS.
• Thorough evaluation of matrix effect.
• Application of developed methods for estuarine waters and WWTP effluents.

In the present work, the suitability of polyethersulfone (PES) tube was assessed for the simultaneous sorptive microextraction of commonly found endocrine disrupting compounds in natural waters such as bisphenol-A (BPA), nonylphenol technical mixture (NP mix), 4-tert-octylphenol (4tOP), 4-n-octylphenol (4-nOP), 17β-estradiol (E2) and 17α-ethynilestradiol (EE2). After the concentration of target compounds in the PES polymer, the analytes were recovered soaking the polymer with a suitable solvent (ethyl acetate or methanol), derivatized using N,O-bis(trimethylsilyl)trifluoroacetamide with 1% of trimethylchlorosilane (BSTFA+1% TMCS) and determined by gas chromatography–mass spectrometry (GC–MS). The analysis was also performed without derivatization step by means of liquid chromatography–tandem mass spectrometry (LC–MS/MS). Extraction parameters (addition of MeOH, ionic strength, extraction speed and time and desorption time) were evaluated and the optimum conditions were fixed as follows: 150 mL water samples containing a 10% (w/v) of sodium chloride and using 5 tubular PES sorbent fibers (1.5 cm length×0.7 mm o.d.). Equilibrium conditions were achieved after 9 h, with absolute extraction efficiencies ranging from 27 to 56%. On the whole, good apparent recoveries were achieved (68–103% and 81–122% for GC–MS and LC–MS/MS, respectively) using deuterated analogues as surrogates. Achieved quantification limits (LOQs) varied between 2–154 ng/L and 2–63 ng/L for all the compounds using GC–MS and LC–MS/MS, respectively. The effect of organic matter was evaluated previous to apply the final method to the analysis of estuarine and wastewater real samples. The comparison of both methods showed that overall, PES-LC–MS/MS provided shorter sample preparation time and better LODs, but PES-silylation-GC–MS allowed the simultaneous determination of all the studied compounds with adequate repeatability and accuracy.

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